Patent GB-477015-A (GB)
Title: An improved process for preparing phenolic derivatives of hydroformed naphthas and products thereof
IPC: C07C37/02
Filed: 1936-06-19
Abstract: Phenols are manufactured from hydroformed naphthas by halogenation and heating under pressure with aqueous alkali, or by sulphonation and fusion with caustic alkali.  The starting materials are produced from petroleum oils of a boiling range including that of gasoline and extending up to about 650-700  DEG F., or from fractions separated therefrom by means of selective solvents, e.g. liquid sulphur dioxide, phenol, acetonitrile, furfurol, o-anisidine, resorcinol diacetate, ethylene diacetate, tricresyl phosphate, triphenyl phosphate, aniline or acetone, by passing them in vapour phase with free hydrogen over catalysts comprising the oxides and/or sulphides of metals of group VI of the periodic table with promoters of the alkaline earth or earth oxide groups, at a pressure exceeding 20 atmospheres, preferably 50-200 atmospheres or higher, and at a temperature above about 900 DEG  F., preferably about 930-1050 DEG F., with a suitable partial pressure of hydrogen and time of contact to secure a destructive hydrogenation without the formation of polymerized or coky material.  The products so obtained may be given a preliminary treatment with a small amount of polymerizing and condensing agents, e.g. sulphuric acid or aluminium chloride, which treatment removes components of high activity and may also be made sufficiently complete to remove substantially all olefines from the naphtha.  In an example, a burning oil fraction boiling at 300-550 DEG  F. is subjected to a solvent extraction with liquid sulphur dioxide, the extract is separated from sulphur dioxide and distilled, and the first 30 per cent distilling is passed with hydrogen at 984 DEG  F. and 3000 lb. per sq. in. pressure over a catalyst containing oxides and sulphides of molybdenum.  The product, or a distillation fraction thereof, e.g. the fraction boiling at 300-400 DEG  F., is sulphonated with concentrated sulphuric acid and the product neutralized with caustic soda and fused with a mixture of sodium and potassium hydroxides.  Alternatively the naphtha is halogenated, e.g. by the action of chlorine at ordinary or raised temperature, and the product is heated under pressure with dilute aqueous sodium hydroxide.  The phenols obtained may be used as preservatives in gasoline, lubricating oils and other hydrocarbon compositions.  The Specification as open to inspection under Sect. 91 comprises also a second method of preparing the starting materials, which involves treatment at lower temperatures of the order of 650-850 DEG  F., preferably about 750 DEG  F., with limited amounts of hydrogen in the presence of catalysts having pronounced cracking activity and relatively slight hydrogenating activity, e.g. a catalyst containing a substantial amount of silica or silicates and a relatively small amount of, for example, the sulphides and oxides of metals of group VI of the periodic system, particularly the sulphides of tungsten and molybdenum.  In an additional example, a cycle gas oil is passed with hydrogen at 3000 lb. per sq. in. pressure over activated clay on which tungsten disulphide has been deposited, at a mean temperature of 729 DEG  F.  This subject-matter does not appear in the Specification as accepted.ALSO:As anti-oxidants in gasoline, lubricating oils and other hydrocarbon compositions may be employed phenols derived from hydroformed naphthas.